EP0030305A1

EP0030305A1 - Chemical pretreatment for method for the electrolytical metal coating of magnesium articles

Info

Publication number: EP0030305A1
Application number: EP80107256A
Authority: EP
Inventors: Asbjorn Ludvig Olsen; Sigbjorn Thomas Halvorsen
Original assignee: Norsk Hydro ASA
Current assignee: Norsk Hydro ASA
Priority date: 1979-12-07
Filing date: 1980-11-20
Publication date: 1981-06-17
Also published as: EP0030305B1; NO793986L; US4349390A; NO145409C; NO145409B; DE3071741D1

Abstract

Improved method of producing of adherent metallic coatings on articles made from magnesium is disclosed. The articles are exposed to a two-step surface activating prior to chemical precipitation of zinc deposit. The first activating is carried out in a solution of oxalic acid and after rinsing a secondary activating takes place in a special bath comprising alkali metal pyrophosphate and preferably added wetting agent. The pyrophosphate is preferably potassium pyrophosphate K₄P₂O₇.

Description

The present invention relates to a method of producing adherent metallic coatings on articles of magnesium and magnesium-base alloys. The invention concerns more particularly an improvement of the known chemical pretreatment process where magnesium articles are coated with metallic zinc and the zinc coating is carried out by chemical reduction, so called contact coating, in a bath containing essentially zinc iones in a complex bonded state with alkali metal pyrophosphate. This method is described in _US Patent no. 2,526,544 and comprises the following main steps:

1. Surface preparation by mechanical pretreatment - machining, polishing, buffing, tumbling, brushing. Degreasing by organic solvents or alkaline cleaning baths followed by pickling in phosphoric acid or in other known pickling solutions for magnesium.
2. Activating of the surface in phoshoric acid and ammonium bifluoride (_US PATENT No. 2,288,995).
3. Chemical zinc coating at 80-85⁰C in a bath consisting of zinc sulpnate, alkali metal pyrophosphate and alkali fluoride.
4. Electrolytical copper strike in a cyanide bath.
5. Standard electrolytical metal coating.

The pretreatment prior to the zinc coating in item 3 is of crucial importance for the quality of the coating itself - adhesion, corrosion resistance and decorative effect of subsequent plated metallic coatings. On this zinc layer any suitable metal can be deposited by electroplating in alkaline baths. Consequently the surface has to be free from oxide and dirt, oil and other contamination. Prior to the deposition of zinc, a thorough cleaning, degreasing and pickling or activating of the metal surface must be carried out.
The known pickling/activating methods have proved to work well . on homogenous materials such as sheets and extrusions, but on castings and especially pressure die castings it is difficult to achieve a satisfactory coating quality. It is assumed that the activating baths applied in the aforementioned patented process, after pickling in a solution of phosphoric acid or other pickling solutions, develop an etched microstructure followed by the formation of Mg F₂ film on or around the intermetallical phases. This results in a chemical/electrochemical surface structure which has an adverse effect on the subsequent contact zinc coating so that the_precipitation of zinc runs unevenly or zone wise. It is therefore necessary to increase the treatment time and/or bath temperature in order to achieve a sufficiently dense zinc deposit over the entire surface. This however involves a local "overzincating", resulting in a porous zinc deposit with a poor mechanical strength which in turn gives poor retention/adhesion of the subsequent metallic coatings. Long treatment time also means higher consumption of chemicals and reduced bath life.
It has been experienced in practice that it is possible to achieve better results by omitting the above mentioned pickling and activating steps in the process. This however requires very efficient mechanical cleaning of the metal surface prior to degreasing and chemical zinc precipitation. In spite of the fact that this modified method has to a certain extent been useful in practice it is not, however, entirely satisfactory. It has been necessary to carry out a very thorough mechanical pretreatment which is more difficult and costly where pressure die cast articles are concerned. Such articles are often of complex design with narrow recesses which are difficult to reach with mechanical treatment.
It has now been surprisingly found out that adherent metallic coatings can be deposited on substrata of magnesium and magnesium alloys without encountering the above mentioned difficulties, by applying a pretreatment as distinctive stated in the characterizing part of the main claim.
It is therefore an object of the present invention to provide a method of producing adherent metallic coatings of high quality on articles made from magnesium and magnesium-base alloys. This technical problem is solved by the inventive method according to claims 1 to 4.
In general the invention consists in providing an adherent metallic coating on the surface of magnesium or magnesium alloy articles and comprises, after mechanical treatment and if necessary cleaning in organical solvents, a two-step activating where the articles are first treated in a solution of oxalic acid, and than rinsed in water and transferred to subsequent activating in a pyrophosphate bath followed by cnemical zinc coating in a manner known per se.
Other characteristics and special features of the invention will be apparent from the following description and examples.
In the first step of the activating of magnesium articles - pickling in an aqueous solution of oxalic acid, oxides and non-metallic inclusions are dissolved and transformed. Reaction products, which are formed on the surface in this step, are easily removed by merely rinsing in water, contrary to currently known pickling processes where other organic or inorganic acids are applied. It has been shown that the reactivity increases in the subsequent treatment in the pyrophosphate bath.
The second activating step consists in activating/deoxidation in an aqueous solution of potassium or sodium pyrophosphate that is added the alkali metal carbonate (Na2C03 or K₂C0₃) in order to achieve the desired pH in the bath. The activating is based upon the ability of the pyrophosphate to dissolve and bind metal oxides and hydroxides by the formation of a complex according to the following main principle:
The formation of magnesium hydroxide proceeds continuously on the metal surface according to the following reaction:
Both these processes will also take place during direct chemical zinc coating without_previous activating because of the excess of pyrophosphate in the bath. Such direct zinc coating has however the disadvantage of the uneven nature of the zinc precipitation process. The most active areas are coated first, while it takes longer time to cover the less active areas with zinc. This is a considerable disadvantage since the treatment time should not exceed 3 minutes with regard to the coating quality and the life of the bath. Besides, the precipitation prosess will be upset by the generated hydrogen.
Activating in accordance with the principles of to the invention has the advantage of achieving uniform zinc precipitation over the entire metal surface. This is of fundamental importance both with respect to the coating quality and the possibilities for process control. Furthermore the precipitation proceeds with negligible or no gas generation. Pyrophosphate activating has also the effect of increasing the reaction rate in the zinc coating process. This is favourable for the process and make it possible to reduce treatment time and lower bath temperature which is an advantage as the environment and energy consumption are concerned and results in increased bath life and a lower consumption of chemicals.

Description of the method

The treatment process comprises basically the following steps:

1. Mechanical pretreatment
2. Degreasing in organic solvents, e.g. trichlorethylene, perchlorethylene or trichlorethan if necessary.
3. Pretreatment/activating. • 3.1. Pickling/activating in oxalic acid 3.2. Activating by means of alkali metal pyrophosphate
4. Chemical zinc precipitation
5. Electrolytical metal coating (Zn, Sn, Cu, Ni, Cr etc.)

Steps 1, 2, 4 and 5 are well known, conventional treatment steps which do not need further explanation.
The appropriate solutions and conditions for the treatment of magnesium articles in step no.3 are as follows:

Step 3.1. - bath composition
After rinsing in water the articles are transferred to step two of the activating process in the deoxidation bath..
Step 3.2 - bath composition

Examples

Pressure cast articles have been pretreated in accordance with the present invention (tests 1-6). As a referance the activating of articles has also been carried out in accordance with the patented process (tests 7-8).

Test 1

1. Activating in oxalic acid solution:

2. Water rinse
3. Activating in pyrophosphate bath:

4. Water rinse
5. Chemical zincating

6. Water rinse
7. Copper strike in alkaline/cyanic bath (Schering/Ultinal) with the following concentrations of copper and free cyanide:

8. Water rinse
9. Nickel plating (Glance nickel bath, Schering "Duplalux G"):

Test 2

Steps 1-2 as Test 1.

3. Activating:

Test 3

Steps 1-2 as Test 1.

3. Activating

Steps 4-9 as Test 1.

Test 4

Steps 1-2 as Test 1.

3. Activating:

Steps 4-9 as Test 1.

Test 5

Steps 1-2 as Test 1.

3. Activating:

Steps 4-9 as Test 1.

Test 6

Steps 1-2 as Test 1.

3. Activating:

Steps 4-9 as Test 1.

Test 7

Activating according to the patented method (reference 1)

3. Pickling in phosphoric acid:

4. Water rinse
5. Activating in phosphoric acid/biofluoride:
6. Water rinse

Further treatment is identical with steps 5-9 in Test 1.
Wetting agent FT 248 is a quaternary ammonium salt of a longchained perfluorated alkane sulphoric acid of Bayer AG, Leverkusen.

Test 8

Direct activating modified according to the patented process (referance 2):

1. Alkaline degreasing as in Test 7.
2. Water rinse
3. Activating in phosphoric acid/bifluoride as step 5 in Test 7.
4. Water rinse

Further treatment identical with steps 5-9 in Test 1.
The quality of the deposit on articles from all tests has been evaluated based against the following criteria:

1. Visual appraisal of the Cu/_Ni deposit immediately after precipitation.
2. Heat test at 150°C for 1 hour with following quenching in water at 20-25⁰C (ISO _R1456 Quenching test for adhesion).

The ealuated samples were divided into four groups:

1. Deposit of good quality, no blistering, good adhesion.
2. Small blisters in the coating.
3. Blister formation and failures in the coating.
4. Extremely poor adhesion.

The results are shown in _Tabel 1.
The tests show clearly that two step activating according to the invention is a better pretreatment method than any of the processes known hitherto.

Claims

1. A method of chemically precipitating a zinc deposit onto articles of magnesium and magnesium-base alloys, where the zinc is used as the base-deposit for the subsequent electrolytical metal coating, characterized i n that the articles after mechanical and/or chemical pretreatment are subject to a two-step surface activating where the first activating in carried out in a solution of oxalic acid and after rinsing, a secondary activating of the articles takes place in a special bath comprising from 10 to 200 g/l alkali metal pyrophosphate, preferably an added wetting agent and as a balance nainly water, after which the articles are rinsed and coated with zinc in the manner known per se.

2. A method according to claim 1, characterized i n that the secondary activating is carried out preferably with potassium pyrophosphate K₄ ^p ₂o₇ in a concentration of from 50-75 g/l as alkali metal pyrophosphate in the bath.

3. A method according to claim 1 or 2, characterized in that the secondary activating is carried out at pH 10-12 and that alkali metal carbonate is applied as buffer.

4. A method according to claim 3, characterized in that the activating is carried out at a bath temperature of 55-65°C.